CN106810578A - A kind of organic phosphorus-nitrogen containing thioesters compound of end sulfydryl and preparation method thereof and obtained fire-retardant polyester fibre POY by its - Google Patents

Abstract

The present invention relates to organic phosphorus-nitrogen containing thioesters compound of a kind of end sulfydryl and preparation method thereof and obtained fire-retardant polyester fibre POY by its, the DAPER that end group is carboxyl is obtained by the phosphorous dicarboxylic acids of side base and the reaction of pentaerythrite first, then one end is obtained for sulfydryl, the other end are the DADA of hydroxyl by holding the nitrogenous monocarboxylic acid of sulfydryl and the reaction of dihydroxylic alcohols, final products are obtained finally by the reaction of DAPER and DADA.Final products are the solid-state carboxylate of HMW, and the end group of molecule is sulfydryl, and the internal P elements containing 15.1~16.04wt%, nitrogen and element sulphur have the advantages that heat endurance is high, widely used.Final products are used to as fire retardant to prepare fire-retardant polyester fibre POY, limited oxygen index >=38% of fire-retardant polyester fibre POY, filament number is 0.3~1.0dtex, fracture strength >=2.1cN/dtex.

Description

A mercapto-terminated organic phosphorus-nitrogen-thio ester compound and its preparation method and its preparation Flame Retardant Polyester Fiber POY Filament

technical field

The invention belongs to the field of flame retardants, and relates to a mercapto-terminated organic phosphorus-nitrogen-thio ester compound, a preparation method thereof, and a flame-retardant polyester fiber POY yarn prepared therefrom, in particular to a solid mercapto-terminated organic phosphorus-containing -Nitrogen-thioester compound and its melt condensation preparation method based on the difference in reactivity of reactants with multifunctional groups.

Background technique

With the development of my country's synthetic material industry and the continuous expansion of application fields, it has been widely used in various fields such as chemical building materials, electronic appliances, transportation, aerospace, daily furniture, interior decoration, basic necessities of life, etc. But most of them are flammable materials, which are easy to cause fire and pose a great threat to life and property safety. Therefore, the flame retardancy of polymer materials has become an urgent problem to be solved. At present, various types of polymers are widely used to add flame retardants to improve the flame retardancy of materials. Phosphorus-based flame retardants have been extensively studied by domestic and foreign experts and scholars for their advantages of high efficiency, low toxicity, and environmental protection.

Chinese patent application publication number CN 101880395A proposes a polymer-type phosphorus-containing flame retardant containing DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) and its preparation method , using DOPO-modified aromatic dihydric phenol or aromatic dihydric alcohol and dichlorinated substituted phosphate as reactants to obtain a polymer-type phosphorus-containing flame retardant, but the phosphorus content of the flame retardant is low, and the process of use The addition of 15% can achieve better flame retardant properties. CN1563152A adopts DOPO-modified hydroquinone or p-naphthalenediol, phenyl or naphthyl-substituted dichloride (bromine) phosphorus oxychloride as reaction substrate to obtain polymer type phosphorus-containing flame retardant, but the flame retardant The amount of precipitating agent used in the separation process is relatively large, and the environmental pollution is relatively large. CN102304230A uses 9,9-bis(4-hydroxyphenyl)fluorene and phenylphosphoryl dichloride or phenoxyphosphoryl dichloride as reaction substrates to prepare phosphorus-containing flame retardants with fluorenyl groups, but the reaction process is relatively complicated , is not easy to control and the solvent required for the experiment needs to be strictly dewatered.

To sum up, most of the flame retardants currently on the market are prepared by solution polymerization. The preparation process has problems such as complicated process, large amount of organic solvent used, difficult solvent recovery and environmental pollution, resulting in high production and processing costs. ; The content of functional elements (P, N, S, etc.) in the flame retardant molecule is low, resulting in low flame retardant efficiency of the flame retardant, and a large amount of flame retardant is required to achieve the ideal flame retardant effect. The addition of a large amount of flame retardant will easily lead to an increase in cost, which will have a negative impact on other properties of the material; most of the flame retardants are liquid compounds with small molecular weight. On the one hand, the low molecular weight of the flame retardant makes the polymerization The compatibility between substances is poor, and the flame retardants are easy to agglomerate in the polymer matrix, and the dispersion is uneven. There are also migration problems during use, resulting in poor durability of flame-retardant products; on the other hand, liquid-type flame-retardant There are difficulties in transportation, storage and processing of pharmaceuticals.

Therefore, it is very important to use a solvent-free method to prepare a solid flame retardant with a high content of functional elements and a relatively large molecular weight.

Contents of the invention

The purpose of the present invention is to overcome the disadvantages of traditional liquid esters such as difficulties in storage and use, environmental pollution during the preparation process, low content of functional elements, and low molecular weight, and to prepare a product with less pollution in the preparation process, high content of functional elements, and low molecular weight. Highly solid mercapto-terminated organic phosphorus-nitrogen-thioester compounds.

In order to achieve the above object, the technical scheme adopted in the present invention is:

A method for preparing a mercapto-terminated organic phosphorus-nitrogen-thio ester compound, the preparation method of the mercapto-terminated organic phosphorus-nitrogen-thio ester compound is a melt condensation method based on the difference in reactivity of the reactant multifunctional group, the reaction The difference in activity means that the multifunctional groups in the reactants have different reactivity due to the influence of steric hindrance. The multifunctional groups undergo condensation reactions in the order of reactivity from high to low. The steps are as follows:

1) Mix side group phosphorus-containing dicarboxylic acid with pentaerythritol in a molar ratio of 4:1, carry out melt esterification reaction under the condition of inert gas protection and mechanical stirring, collect the product, and obtain terminal group as carboxyl group after post-treatment DAPER; the reactivity of the two carboxylic acid groups of the side group phosphorus-containing dicarboxylic acid is different, and the structural formula of the side group phosphorus-containing dicarboxylic acid is:

2) Mix the thiol-terminated nitrogen-containing monocarboxylic acid and the dihydric alcohol at a molar ratio of 1:1, add a catalyst, and perform a melt condensation reaction under the protection of an inert gas and mechanical stirring to obtain a mercapto group at one end and a hydroxyl group at the other end DADA; the reactivity of the sulfhydryl group and the carboxylic acid group in the sulfhydryl-terminated nitrogen-containing monocarboxylic acid is different;

3) Add the DAPER obtained in step 1) to the system in step 2), the molar ratio of DAPER to DADA is 1:4, keep the temperature of the system constant, continue to feed inert gas, under the condition of mechanical stirring The melt esterification reaction is carried out, the product is collected, and the terminal mercapto group organic phosphorus-nitrogen-thio ester compound is obtained after post-processing.

As a preferred technical solution:

In the method for preparing a mercapto-terminated organic phosphorus-nitrogen-thio ester compound as described above, in step 1), the inert gas is nitrogen or argon, and the stirring speed of the mechanical stirring is 300-500 rpm; The temperature of the melt esterification reaction is 180-200° C., and the reaction time is 1-4 hours; the post-processing includes dissolving, filtering and drying.

A method for preparing a mercapto-terminated organic phosphorus-nitrogen-thio ester compound as described above, the structural formula of the mercapto-terminated nitrogen-containing monocarboxylic acid is:

The dihydric alcohol is ethylene glycol, propylene glycol or 1,4-butanediol.

A method for preparing a mercapto-terminated organic phosphorus-nitrogen-thio ester compound as described above, in step 2), the catalyst is 4-methylbenzenesulfonic acid, and the mercapto-terminated nitrogen-containing monocarboxylic acid and the catalyst The molar ratio is 1:0.01, the inert gas is nitrogen or argon, the stirring speed of the mechanical stirring is 300-500rpm, the temperature of the melting condensation reaction is 180-200°C, and the reaction time is 1-3h.

In the method for preparing a mercapto-terminated organic phosphorus-nitrogen-thio ester compound as described above, in step 3), the inert gas is nitrogen or argon, and the stirring speed of the mechanical stirring is 300-500rpm. The time for the melt esterification reaction is 1-4 hours, and the post-treatment includes crushing, dissolving, filtering, washing and drying.

According to the method for preparing a mercapto-terminated organic phosphorus-nitrogen-thio ester compound, the drying refers to vacuum drying in a vacuum oven at 25-50° C. for 6-18 hours.

The present invention also provides a mercapto-terminated organic phosphorus-nitrogen-thio ester compound, the mercapto-terminated organic phosphorus-nitrogen-thio ester compound is a solid ester compound, and the mercapto-terminated organic phosphorus-nitrogen-thio ester compound The molecular structure formula is as follows:

In the formula, It represents the chain segment between the quaternary carbon C and R in the molecular center of the mercapto-terminal organic phosphorus-nitrogen-thioester compound. The -CH ₂ - in the chain segment is connected to the quaternary carbon C in the molecular center of the ester compound. The specific structural formula is as follows:

The R is a nitrogen-sulfur long chain whose terminal group is a mercapto group;

The total content of phosphorus element, nitrogen element and sulfur element in the molecule of the mercapto-terminated organic phosphorus-nitrogen-thio ester compound is 15.1-16.04wt%.

As a preferred technical solution:

As described above, a thiol-terminated organic phosphorus-nitrogen-thio ester compound, the structural formula of the nitrogen-sulfur long chain whose end group is a mercapto group is as follows:

Among them, n=2,3,4.

A mercapto-terminated organic phosphorus-nitrogen-thio ester compound as described above, the molecular weight of the mercapto-terminated organic phosphorus-nitrogen-thio ester compound is 1920-2040 g/mol, the melting point is 65-125 °C, and the initial heat The decomposition temperature is 340-420°C.

The present invention also provides a kind of flame-retardant polyester fiber POY yarn made from mercapto-terminated organic phosphorus-nitrogen-thio ester compounds. The preparation steps of flame-retardant polyester fiber POY yarn are as follows:

(1) Melt blending, the dried mercapto-terminated organic phosphorus-nitrogen-thioester compound is mixed with PET chips to obtain a premix, and the premix is melt-blended and sliced to obtain flame-retardant polyester chips;

(2) Melt spinning, the dried flame-retardant polyester chips are measured, extruded, cooled, oiled and wound to obtain flame-retardant polyester fiber POY filaments.

The above-mentioned flame-retardant polyester fiber POY yarn, the melt blending is carried out in a twin-screw extruder, and the mass ratio of the mercapto-terminated organic phosphorus-nitrogen-thioester compound to the PET chips during the melt blending is 3～10:90～97, the temperature of described melt blending is 255～265 ℃;

The technological parameter of described melt spinning is:

Extrusion temperature: 280-290°C;

Cooling temperature: 20-30°C;

Winding speed: 2500-3500m/min;

The limiting oxygen index of the flame-retardant polyester fiber POY filament is ≥38%, the single filament fineness is 0.3-1.0dtex, the breaking strength is ≥2.1cN/dtex, and the breaking elongation is 110.0±10.0%.

The esterified product prepared by the present invention is a solid mercapto-terminated organic phosphorus-nitrogen-thio ester compound prepared by a melt condensation method based on the difference in reactivity of the multifunctional groups of the reactants, and the reaction process mainly depends on the difference in the reactivity of the multifunctional groups of the reactants. The raw material used in the first step of the reaction is a side-group phosphorus-containing dicarboxylic acid, and the two carboxyl groups -COOH in the side-group phosphorus-containing dicarboxylic acid molecule are connected to the same tertiary carbon directly or through a methylene group -CH ₂ - , due to the larger structure of the side group phosphorus-containing group will produce steric hindrance effect, the reactivity of the carboxyl-COOH connected to the tertiary carbon through the methylene-CH ₂ - in the side-group phosphorus-containing dicarboxylic acid molecule is higher than that of the direct The carboxyl-COOH connected to the tertiary carbon, during the esterification reaction, the carboxyl-COOH connected to the methylene-CH ₂ - can undergo esterification reaction before the hydroxyl-OH in pentaerythritol to form an ester bond, and because the side group The molar ratio of phosphorus-containing dicarboxylic acid to pentaerythritol is 4:1, and what occurs between the two is a capping reaction, so the reaction between the highly reactive -COOH in the side group phosphorus-containing dicarboxylic acid and the -OH in pentaerythritol ends After that, it stops, and the end group of the generated mercapto-terminated organic phosphorus-nitrogen-thioester compound is the carboxyl-COOH with low reactivity in the primary side group phosphorus-containing dicarboxylic acid molecule, and the carboxyl-COOH is used as a reactive group Participate in subsequent responses.

In the second step reaction process, there is a difference in the reactivity of the two functional groups (mercapto and carboxylic acid groups) due to the steric hindrance effect of the nitrogen-containing monocarboxylic acid at the end of the thiol group. When the mole of the nitrogen-containing monocarboxylic acid at the end of the mercapto group and the glycol When the ratio is 1:1, the highly reactive carboxylic acid group in the mercapto-terminated nitrogen-containing monocarboxylic acid undergoes a condensation reaction with the hydroxyl-OH in the dibasic alcohol, and the resulting esterified product has a hydroxyl-OH at one end and a proto-OH at the other end. The less reactive sulfhydryl group in nitrogen-containing monocarboxylic acid molecules.

In the third step reaction process, the carboxyl-COOH of the product end group of the first step reaction and the hydroxyl group-OH of the product end group of the second step reaction further undergo an esterification reaction to obtain a mercapto-terminated organic phosphorus-nitrogen-thioester compound . Beneficial effect:

1) The esterified product prepared by the present invention is a solid-type mercapto-terminated organic phosphorus-nitrogen-thio esterified product, which overcomes the disadvantages of difficult addition and storage when the traditional liquid-type esterified product is used as an additive;

2) The end group of the organic phosphorus-nitrogen-thioester compound prepared by the present invention contains abundant mercapto groups, and its molecular structure can be designed to prepare a multifunctional compound as a reaction monomer for further reactions;

3) The mercapto-terminated organic phosphorus-nitrogen-thioester compound obtained in the present invention has a higher molecular weight (1920-2040g/mol) and a star structure. When used as an additive, it can improve the compatibility with the polymer, Overcome the problems of easy migration and poor durability of small molecular weight additives;

4) When the mercapto-terminated organic phosphorus-nitrogen-thio ester compound prepared by the present invention is used as a functional additive, it has good compatibility with the polymer matrix, due to the high content of phosphorus, nitrogen and sulfur (15.1～ 16.04wt%), a better modification effect can be achieved when the addition amount is less (less than 5wt%);

5) The thiol-terminated organic phosphorus-nitrogen-thio ester compound prepared by the present invention contains phosphorus, nitrogen and sulfur at the same time, and can play a good synergistic effect;

6) The method for preparing mercapto-terminated organic phosphorus-nitrogen-thio esters is simple, belongs to melt condensation, does not need to use a large amount of solvent, does not affect the environment, is beneficial to environmental protection, and reduces solvent recovery costs.

detailed description

The present invention will be further described below in combination with specific embodiments. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the teachings of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.

Example 1

A method for preparing a mercapto-terminated organic phosphorus-nitrogen-thioester compound, the steps are as follows:

1) The side group phosphorus-containing dicarboxylic acid and pentaerythritol are mixed with a molar ratio of 4:1, and the melt esterification reaction is carried out under the conditions of nitrogen protection and mechanical stirring. The stirring speed of the mechanical stirring is 300rpm, and the melting esterification reaction The temperature is 180°C, and the reaction time is 1 hour. After the reaction, the product is collected, dissolved, filtered and dried to obtain DAPER with a carboxyl group at the end. The structural formula of the side group phosphorus-containing dicarboxylic acid is:

2) Mix the thiol-terminated nitrogen-containing monocarboxylic acid and ethylene glycol at a molar ratio of 1:1, add 4-methylbenzenesulfonic acid, the molar ratio of the mercapto-terminal nitrogen-containing monocarboxylic acid to 4-methylbenzenesulfonic acid The ratio is 1:0.01, and the melting condensation reaction is carried out under the conditions of argon protection and mechanical stirring. The stirring speed of mechanical stirring is 300rpm, the temperature of the melting condensation reaction is 180°C, and the reaction time is 1h. One end is mercapto and the other end is Hydroxyl DADA, in which the structural formula of the thiol-terminated nitrogen-containing monocarboxylic acid is:

3) Add the DAPER obtained in step 1) to the system in step 2), the molar ratio of DAPER to DADA is 1:4, keep the temperature of the system constant, continue to feed argon, under the condition of mechanical stirring Carry out the melt esterification reaction, the stirring speed of the mechanical stirring is 300rpm, the time of the melt esterification reaction is 1h, the product is collected, pulverized, dissolved, filtered, washed and dried in a vacuum oven at 25°C for 6h to obtain a mercapto-terminated organic compound containing Phosphorus-nitrogen-thioesters.

The molecular structural formula of the finally prepared thiol-terminated organic phosphorus-nitrogen-thioester compound is as follows:

In the formula, It represents the chain segment between the quaternary carbon C and R in the molecular center of the mercapto-terminal organic phosphorus-nitrogen-thioester compound. The -CH ₂ - in the chain segment is connected to the quaternary carbon C in the molecular center of the ester compound. The specific structural formula is as follows:

The structural formula of R is as follows:

Among them, n=2.

The total content of phosphorus, nitrogen and sulfur in the finally obtained mercapto-terminated organic phosphorus-nitrogen-thioester compound molecule is 15.98wt%, and the molecular weight of the mercapto-terminated organic phosphorus-nitrogen-thioester compound is 1928g/mol. The melting point is 65°C, and the initial thermal decomposition temperature is 412°C.

Example 2

A method for preparing a mercapto-terminated organic phosphorus-nitrogen-thioester compound, the steps are as follows:

1) The side group phosphorus-containing dicarboxylic acid and pentaerythritol are mixed with a molar ratio of 4:1, and the melt esterification reaction is carried out under the conditions of nitrogen protection and mechanical stirring, and the stirring speed of the mechanical stirring is 336rpm. The temperature is 185°C, and the reaction time is 1 hour. After the reaction, the product is collected, dissolved, filtered and dried to obtain DAPER with a carboxyl group at the end. The structural formula of the side group phosphorus-containing dicarboxylic acid is:

2) Mix the mercapto-terminated nitrogen-containing monocarboxylic acid and propylene glycol at a molar ratio of 1:1, add 4-methylbenzenesulfonic acid, and the molar ratio of the mercapto-terminal nitrogen-containing monocarboxylic acid to 4-methylbenzenesulfonic acid is 1 : 0.01, under the condition of argon protection and mechanical stirring, carry out melting condensation reaction, the stirring speed of mechanical stirring is 336rpm, the temperature of melting condensation reaction is 185 ℃, and the reaction time is 1h, obtain one end to be mercapto, the other end is hydroxyl DADA, in which the structural formula of thiol-terminated nitrogen-containing monocarboxylic acid is:

3) Add the DAPER obtained in step 1) to the system in step 2), the molar ratio of DAPER to DADA is 1:4, keep the temperature of the system constant, continue to feed argon, under the condition of mechanical stirring Carry out the melt esterification reaction, the stirring speed of the mechanical stirring is 336rpm, the time of the melt esterification reaction is 1h, the product is collected, pulverized, dissolved, filtered, washed and dried in a vacuum oven at 28°C for 10h to obtain a mercapto-terminated organic compound containing Phosphorus-nitrogen-thioesters.

The molecular structural formula of the finally prepared thiol-terminated organic phosphorus-nitrogen-thioester compound is as follows:

In the formula, It represents the chain segment between the quaternary carbon C and R in the molecular center of the mercapto-terminal organic phosphorus-nitrogen-thioester compound. The -CH ₂ - in the chain segment is connected to the quaternary carbon C in the molecular center of the ester compound. The specific structural formula is as follows:

The structural formula of R is as follows:

Among them, n=3.

The total content of phosphorus, nitrogen and sulfur in the finally obtained mercapto-terminated organic phosphorus-nitrogen-thioester compound molecule is 15.52wt%, and the molecular weight of the mercapto-terminated organic phosphorus-nitrogen-thioester compound is 1984g/mol. The melting point is 87°C, and the initial thermal decomposition temperature is 373°C.

Example 3

A method for preparing a mercapto-terminated organic phosphorus-nitrogen-thioester compound, the steps are as follows:

1) The side group phosphorus-containing dicarboxylic acid and pentaerythritol are mixed with a molar ratio of 4:1, and the melt esterification reaction is carried out under the conditions of nitrogen protection and mechanical stirring, and the stirring speed of the mechanical stirring is 345rpm. The temperature is 188°C, and the reaction time is 1 hour. After the reaction, the product is collected, dissolved, filtered and dried to obtain DAPER with a carboxyl group at the end. The structural formula of the side group phosphorus-containing dicarboxylic acid is:

2) Mix thiol-terminated nitrogen-containing monocarboxylic acid and 1,4-butanediol at a molar ratio of 1:1, add 4-methylbenzenesulfonic acid, mercapto-terminated nitrogen-containing monocarboxylic acid and 4-methylbenzenesulfonic acid The molar ratio of the acid is 1:0.01, the melt condensation reaction is carried out under the conditions of argon protection and mechanical stirring, the stirring speed of the mechanical stirring is 345rpm, the temperature of the melt condensation reaction is 188°C, and the reaction time is 1h, and one end is mercapto , DADA with a hydroxyl group at the other end, wherein the structural formula of a nitrogen-containing monocarboxylic acid with a mercapto group is:

3) Add the DAPER obtained in step 1) to the system in step 2), the molar ratio of DAPER to DADA is 1:4, keep the temperature of the system constant, continue to feed argon, under the condition of mechanical stirring Carry out the melt esterification reaction, the stirring speed of the mechanical stirring is 345rpm, the time of the melt esterification reaction is 2h, the product is collected, pulverized, dissolved, filtered, washed and dried in a vacuum oven at 30°C for 12h to obtain a mercapto-terminated organic compound containing Phosphorus-nitrogen-thioesters.

The molecular structural formula of the finally prepared thiol-terminated organic phosphorus-nitrogen-thioester compound is as follows:

In the formula, It represents the chain segment between the quaternary carbon C and R in the molecular center of the mercapto-terminal organic phosphorus-nitrogen-thioester compound. The -CH ₂ - in the chain segment is connected to the quaternary carbon C in the molecular center of the ester compound. The specific structural formula is as follows:

The structural formula of R is as follows:

Among them, n=4.

The total content of phosphorus, nitrogen and sulfur in the finally obtained mercapto-terminated organic phosphorus-nitrogen-thioester compound molecule is 15.1wt%, and the molecular weight of the mercapto-terminated organic phosphorus-nitrogen-thioester compound is 2040g/mol. The melting point is 98°C, and the initial thermal decomposition temperature is 340°C.

Example 4

A method for preparing a mercapto-terminated organic phosphorus-nitrogen-thioester compound, the steps are as follows:

1) The side group phosphorus-containing dicarboxylic acid and pentaerythritol are mixed with a molar ratio of 4:1, and the melt esterification reaction is carried out under the conditions of nitrogen protection and mechanical stirring, and the stirring speed of the mechanical stirring is 358rpm. The temperature is 188°C, and the reaction time is 2 hours. After the reaction, the product is collected, dissolved, filtered and dried to obtain DAPER whose end group is carboxyl group. The structural formula of the side group phosphorus-containing dicarboxylic acid is:

2) Mix the thiol-terminated nitrogen-containing monocarboxylic acid and ethylene glycol at a molar ratio of 1:1, add 4-methylbenzenesulfonic acid, the molar ratio of the mercapto-terminal nitrogen-containing monocarboxylic acid to 4-methylbenzenesulfonic acid The ratio is 1:0.01, and the melting condensation reaction is carried out under the conditions of argon protection and mechanical stirring. The stirring speed of the mechanical stirring is 358rpm, the temperature of the melting condensation reaction is 190°C, and the reaction time is 2h. One end is a mercapto group and the other end is a Hydroxyl DADA, in which the structural formula of the thiol-terminated nitrogen-containing monocarboxylic acid is:

3) Add the DAPER obtained in step 1) to the system in step 2), the molar ratio of DAPER to DADA is 1:4, keep the temperature of the system constant, continue to feed argon, under the condition of mechanical stirring Carry out the melt esterification reaction, the stirring speed of the mechanical stirring is 358rpm, the time of the melt esterification reaction is 2h, the product is collected, pulverized, dissolved, filtered, washed and dried in a vacuum oven at 35°C for 14h to obtain a mercapto-terminated organic compound containing Phosphorus-nitrogen-thioesters.

The molecular structural formula of the finally prepared thiol-terminated organic phosphorus-nitrogen-thioester compound is as follows:

In the formula, It represents the chain segment between the quaternary carbon C and R in the molecular center of the mercapto-terminal organic phosphorus-nitrogen-thioester compound. The -CH ₂ - in the chain segment is connected to the quaternary carbon C in the molecular center of the ester compound. The specific structural formula is as follows:

The structural formula of R is as follows:

Among them, n=2.

The total content of phosphorus, nitrogen and sulfur in the finally obtained mercapto-terminated organic phosphorus-nitrogen-thioester compound molecule is 16.04wt%, and the molecular weight of the mercapto-terminated organic phosphorus-nitrogen-thioester compound is 1920g/mol. The melting point is 105°C, and the initial thermal decomposition temperature is 420°C.

Example 5

A method for preparing a mercapto-terminated organic phosphorus-nitrogen-thioester compound, the steps are as follows:

1) The side group phosphorus-containing dicarboxylic acid and pentaerythritol are mixed with a molar ratio of 4:1, and the melt esterification reaction is carried out under nitrogen protection and mechanical stirring. The stirring speed of the mechanical stirring is 386rpm, and the melting esterification reaction The temperature is 190°C, and the reaction time is 3 hours. After the reaction is completed, the product is collected, dissolved, filtered and dried to obtain DAPER with a carboxyl group at the end. The structural formula of the side group phosphorus-containing dicarboxylic acid is:

2) Mix the mercapto-terminated nitrogen-containing monocarboxylic acid and propylene glycol at a molar ratio of 1:1, add 4-methylbenzenesulfonic acid, and the molar ratio of the mercapto-terminal nitrogen-containing monocarboxylic acid to 4-methylbenzenesulfonic acid is 1 : 0.01, under the condition of argon protection and mechanical stirring, carry out melting condensation reaction, the stirring speed of mechanical stirring is 386rpm, the temperature of melting condensation reaction is 195 ℃, and the reaction time is 3h, obtain one end as mercapto group, the other end is hydroxyl DADA, in which the structural formula of thiol-terminated nitrogen-containing monocarboxylic acid is:

3) Add the DAPER obtained in step 1) to the system in step 2), the molar ratio of DAPER to DADA is 1:4, keep the temperature of the system constant, continue to feed argon, under the condition of mechanical stirring Carry out the melt esterification reaction, the stirring speed of the mechanical stirring is 386rpm, the time of the melt esterification reaction is 3h, the product is collected, pulverized, dissolved, filtered, washed and dried in a vacuum oven at 40°C for 15h to obtain a mercapto-terminated organic compound Phosphorus-nitrogen-thioesters.

The molecular structural formula of the finally prepared thiol-terminated organic phosphorus-nitrogen-thioester compound is as follows:

In the formula, It represents the chain segment between the quaternary carbon C and R in the molecular center of the mercapto-terminal organic phosphorus-nitrogen-thioester compound. The -CH ₂ - in the chain segment is connected to the quaternary carbon C in the molecular center of the ester compound. The specific structural formula is as follows:

The structural formula of R is as follows:

Among them, n=3.

The total content of phosphorus, nitrogen and sulfur in the finally obtained mercapto-terminated organic phosphorus-nitrogen-thioester compound molecule is 15.59wt%, and the molecular weight of the mercapto-terminated organic phosphorus-nitrogen-thioester compound is 1976g/mol. The melting point is 112°C, and the initial thermal decomposition temperature is 375°C.

Example 6

A method for preparing a mercapto-terminated organic phosphorus-nitrogen-thioester compound, the steps are as follows:

1) The side group phosphorus-containing dicarboxylic acid and pentaerythritol are mixed with a molar ratio of 4:1, and the melt esterification reaction is carried out under the conditions of nitrogen protection and mechanical stirring, and the stirring speed of the mechanical stirring is 500rpm. The temperature is 200°C, and the reaction time is 4 hours. After the reaction is completed, the product is collected, dissolved, filtered and dried to obtain DAPER with a carboxyl group at the end. The structural formula of the side group phosphorus-containing dicarboxylic acid is:

2) Mix thiol-terminated nitrogen-containing monocarboxylic acid and 1,4-butanediol at a molar ratio of 1:1, add 4-methylbenzenesulfonic acid, mercapto-terminated nitrogen-containing monocarboxylic acid and 4-methylbenzenesulfonic acid The molar ratio of the acid is 1:0.01, and the melting condensation reaction is carried out under the conditions of argon protection and mechanical stirring. The stirring speed of the mechanical stirring is 500 rpm, the temperature of the melting condensation reaction is 200 ° C, and the reaction time is 3 hours. , DADA with a hydroxyl group at the other end, wherein the structural formula of a nitrogen-containing monocarboxylic acid with a mercapto group is:

3) Add the DAPER obtained in step 1) to the system in step 2), the molar ratio of DAPER to DADA is 1:4, keep the temperature of the system constant, continue to feed argon, under the condition of mechanical stirring Carry out the melt esterification reaction, the stirring speed of the mechanical stirring is 500rpm, the time of the melt esterification reaction is 4h, the product is collected, pulverized, dissolved, filtered, washed and dried in a vacuum oven at 50°C for 18h to obtain a mercapto-terminated organic compound containing Phosphorus-nitrogen-thioesters.

The molecular structural formula of the finally prepared thiol-terminated organic phosphorus-nitrogen-thioester compound is as follows:

In the formula, It represents the chain segment between the quaternary carbon C and R in the molecular center of the mercapto-terminal organic phosphorus-nitrogen-thioester compound. The -CH ₂ - in the chain segment is connected to the quaternary carbon C in the molecular center of the ester compound. The specific structural formula is as follows:

The structural formula of R is as follows:

Among them, n=4.

The total content of phosphorus, nitrogen and sulfur in the finally obtained mercapto-terminated organic phosphorus-nitrogen-thioester compound molecule is 15.16wt%, and the molecular weight of the mercapto-terminated organic phosphorus-nitrogen-thioester compound is 2032g/mol. The melting point is 125°C, and the initial thermal decomposition temperature is 349°C.

Example 7

A flame-retardant polyester fiber POY yarn, the preparation steps are as follows:

(1) Melt blending, the dried mercapto-terminated organic phosphorus-nitrogen-thioester compound obtained in Example 1 is mixed with PET chips to obtain a premix, wherein the mercapto-terminated organic phosphorus-nitrogen-thioester compound The mass ratio to PET chips is 3:97, and the premixed material is melt-blended in a twin-screw extruder at 255°C and then sliced to obtain flame-retardant polyester chips;

(2) Melt spinning, the flame retardant polyester chips after drying are measured, extruded, cooled, oiled and wound to obtain flame retardant polyester fiber POY filaments. The process parameters of melt spinning are:

Extrusion temperature: 280°C;

Cooling temperature: 20°C;

Winding speed: 2500m/min.

The limiting oxygen index of the finally prepared flame-retardant polyester fiber POY filament is 38%, the single filament fineness is 0.3dtex, the breaking strength is 2.1cN/dtex, and the breaking elongation is 100%.

Example 8

A flame-retardant polyester fiber POY yarn, the preparation steps are as follows:

(1) Melt blending, the dried mercapto-terminated organic phosphorus-nitrogen-thioester compound obtained in Example 2 is mixed with PET chips to obtain a premix, wherein the mercapto-terminated organic phosphorus-nitrogen-thioester compound The mass ratio to PET chips is 5:95, and the premixed material is melt-blended in a twin-screw extruder at 257°C and then sliced to obtain flame-retardant polyester chips;

(2) Melt spinning, the flame retardant polyester chips after drying are measured, extruded, cooled, oiled and wound to obtain flame retardant polyester fiber POY filaments. The process parameters of melt spinning are:

Extrusion temperature: 282°C;

Cooling temperature: 22°C;

Winding speed: 2700m/min.

The limiting oxygen index of the finally prepared flame-retardant polyester fiber POY filament is 38.8%, the single filament fineness is 0.4dtex, the breaking strength is 2.3cN/dtex, and the breaking elongation is 104%.

Example 9

A flame-retardant polyester fiber POY yarn, the preparation steps are as follows:

(1) Melt blending, the dried mercapto-terminated organic phosphorus-nitrogen-thioester compound obtained in Example 3 is mixed with PET chips to obtain a premix, wherein the mercapto-terminated organic phosphorus-nitrogen-thioester compound The mass ratio to PET chips is 6:94, and the premixed material is melt-blended in a twin-screw extruder at 259°C and then sliced to obtain flame-retardant polyester chips;

(2) Melt spinning, the flame retardant polyester chips after drying are measured, extruded, cooled, oiled and wound to obtain flame retardant polyester fiber POY filaments. The process parameters of melt spinning are:

Extrusion temperature: 284°C;

Cooling temperature: 24°C;

Winding speed: 2900m/min.

The limiting oxygen index of the finally prepared flame-retardant polyester fiber POY filament is 39.5%, the single filament fineness is 0.5dtex, the breaking strength is 2.4cN/dtex, and the breaking elongation is 108%.

Example 10

A flame-retardant polyester fiber POY yarn, the preparation steps are as follows:

(1) Melt blending, the dried mercapto-terminated organic phosphorus-nitrogen-thioester compound obtained in Example 4 is mixed with PET chips to obtain a premix, wherein the mercapto-terminated organic phosphorus-nitrogen-thioester compound The mass ratio to PET chips is 8:92, and the premixed material is melt-blended in a twin-screw extruder at 261°C and then sliced to obtain flame-retardant polyester chips;

(2) Melt spinning, the flame retardant polyester chips after drying are measured, extruded, cooled, oiled and wound to obtain flame retardant polyester fiber POY filaments. The process parameters of melt spinning are:

Extrusion temperature: 286°C;

Cooling temperature: 26°C;

Winding speed: 3100m/min.

The limiting oxygen index of the finally prepared flame-retardant polyester fiber POY filament is 39.9%, the single filament fineness is 0.55dtex, the breaking strength is 2.5cN/dtex, and the breaking elongation is 112%.

Example 11

A flame-retardant polyester fiber POY yarn, the preparation steps are as follows:

(1) Melt blending, the dried mercapto-terminated organic phosphorus-nitrogen-thioester compound obtained in Example 5 is mixed with PET chips to obtain a premix, wherein the mercapto-terminated organic phosphorus-nitrogen-thioester compound The mass ratio to PET chips is 9:91, and the premixed material is melt-blended in a twin-screw extruder at 263°C and then sliced to obtain flame-retardant polyester chips;

(2) Melt spinning, the flame retardant polyester chips after drying are measured, extruded, cooled, oiled and wound to obtain flame retardant polyester fiber POY filaments. The process parameters of melt spinning are:

Extrusion temperature: 288°C;

Cooling temperature: 28°C;

Winding speed: 3300m/min.

The limiting oxygen index of the finally prepared flame-retardant polyester fiber POY filament is 40.5%, the single filament fineness is 0.6dtex, the breaking strength is 2.6cN/dtex, and the breaking elongation is 116%.

Example 12

A flame-retardant polyester fiber POY yarn, the preparation steps are as follows:

(1) Melt blending, the dried mercapto-terminated organic phosphorus-nitrogen-thioester compound obtained in Example 6 is mixed with PET chips to obtain a premix, wherein the mercapto-terminated organic phosphorus-nitrogen-thioester compound The mass ratio to PET chips is 10:90, and the premixed material is melt-blended in a twin-screw extruder at 265°C and then sliced to obtain flame-retardant polyester chips;

(2) Melt spinning, the flame retardant polyester chips after drying are measured, extruded, cooled, oiled and wound to obtain flame retardant polyester fiber POY filaments. The process parameters of melt spinning are:

Extrusion temperature: 290°C;

Cooling temperature: 30°C;

Winding speed: 3500m/min.

The limiting oxygen index of the finally prepared flame-retardant polyester fiber POY filament is 40.9%, the single filament fineness is 1.0dtex, the breaking strength is 2.8cN/dtex, and the breaking elongation is 120%.

Claims (10)

1. the preparation method of the organic containing phosphorus-nitrogen of a kind of end sulfydryl-thioesters compound, it is characterized in that, the end sulfydryl it is organic it is phosphorous- The preparation method of nitrogen-thioesters compound is the melt condensation method based on reactant polyfunctional group reactivity difference, and the reaction is lived Sex differernce refers to that polyfunctional group in reactant is influenceed have different reactivities by steric hindrance, polyfunctional group according to There is condensation reaction in reactivity order from high to low, step is as follows：

1) by the phosphorous dicarboxylic acids of side base and pentaerythrite with 4:1 mixed in molar ratio, in inert gas shielding and mechanical agitation Under conditions of carry out fusion esterification reaction, collect product, it is post-treated to obtain the DAPER that end group is carboxyl；The side base is phosphorous The reactivity of two carboxylic acid groups of dicarboxylic acids is different, and the structural formula of the phosphorous dicarboxylic acids of side base is：

2) by the nitrogenous monocarboxylic acid of end sulfydryl and dihydroxylic alcohols with 1:1 mixed in molar ratio, adds catalyst, in inert gas shielding With melt condensation reaction is carried out under conditions of mechanical agitation, obtain one end for sulfydryl, the other end for hydroxyl DADA；The end mercapto Sulfydryl is different with the reactivity of carboxylic acid group in the nitrogenous monocarboxylic acid of base；

3) by step 1) in the DAPER that obtains be added to step 2) in system in, the mol ratio of DAPER and DADA is 1:4, protect The temperature-resistant of system is held, inert gas is continually fed into, fusion esterification reaction is carried out under conditions of mechanical agitation, collected and produce Thing, it is post-treated to obtain the organic containing phosphorus-nitrogen of end sulfydryl-thioesters compound.

2. the preparation method of the organic containing phosphorus-nitrogen of a kind of end sulfydryl-thioesters compound according to claim 1, it is characterised in that Step 1) in, the inert gas is nitrogen or argon gas, and the churned mechanically mixing speed is 300~500rpm；It is described molten It is 180~200 DEG C to melt the temperature of esterification, and the reaction time is 1~4h；The post processing includes dissolving, filtering and dries.

3. the preparation method of the organic containing phosphorus-nitrogen of a kind of end sulfydryl-thioesters compound according to claim 1, it is characterised in that The nitrogenous monocarboxylic structural formula of end sulfydryl is：

The dihydroxylic alcohols is ethylene glycol, propane diols or 1,4- butanediols.

4. the preparation method of the organic containing phosphorus-nitrogen of a kind of end sulfydryl-thioesters compound according to claim 1, it is characterised in that Step 2) in, the catalyst is 4- toluene sulfonic acides, and the nitrogenous monocarboxylic acid of end sulfydryl is 1 with the mol ratio of catalyst: 0.01, the inert gas is nitrogen or argon gas, and the churned mechanically mixing speed is 300~500rpm, the melting contracting The temperature for closing reaction is 180~200 DEG C, and the reaction time is 1~3h.

5. the preparation method of the organic containing phosphorus-nitrogen of a kind of end sulfydryl-thioesters compound according to claim 1, it is characterised in that Step 3) in, the inert gas is nitrogen or argon gas, and the churned mechanically mixing speed is 300~500rpm, described molten Melt the time of esterification for 1~4h, the post processing includes crushing, dissolving, being filtered, washed and dried, and the drying refers to 6~18h of vacuum drying in 25~50 DEG C of vacuum drying oven.

6. using a kind of organic containing phosphorus-nitrogen-thioesters of end sulfydryl obtained in the preparation method as described in any one of Claims 1 to 5 Compound, it is characterized in that：The organic containing phosphorus-nitrogen of the end sulfydryl-thioesters compound is solid-state carboxylate, the end sulfydryl it is organic it is phosphorous- The molecular structural formula of nitrogen-thioesters compound is as follows：

In formula,The segment between the quaternary carbon C and R of the organic containing phosphorus-nitrogen of end sulfydryl-thioesters compound molecular center is represented, in segment - CH₂- be connected with the quaternary carbon C of carboxylate molecular center, concrete structure formula is as follows：

The R is that end group is the nitrogenous-sulphur long-chain of sulfydryl；

In the organic containing phosphorus-nitrogen of the end sulfydryl-thioesters compound molecule total content of P elements, nitrogen and element sulphur be 15.1~ 16.04wt%.

7. the organic containing phosphorus-nitrogen of a kind of end sulfydryl-thioesters compound according to claim 6, it is characterised in that the end group is The structural formula of the nitrogenous-sulphur long-chain of sulfydryl is as follows：

Wherein, n=2,3,4.

8. a kind of organic containing phosphorus-nitrogen of end sulfydryl-thioesters compound according to claim 6, it is characterised in that the end sulfydryl The molecular weight of organic containing phosphorus-nitrogen-thioesters compound is 1920~2040g/mol, and fusing point is 65~125 DEG C, initial heat decomposition temperature It is 340~420 DEG C.

9. one kind fire-retardant polyester fibre POY as obtained in holding the organic containing phosphorus-nitrogen of sulfydryl-thioesters compound as claimed in claim 6 Silk, it is characterized in that, the preparation process of fire-retardant polyester fibre POY is as follows：

(1) melt blending, the organic containing phosphorus-nitrogen of dried end sulfydryl-thioesters compound and PET sections are carried out being mixed to get premix Material, flame retardant polyester section is obtained by being cut into slices after premix melt blending；

(2) melt spinning, dried flame retardant polyester section is obtained flame retardant polyester fibre through measuring, extruding, cool down, oil and wind Dimension POY.

10. fire-retardant polyester fibre POY according to claim 9, it is characterised in that the melt blending is in twin-screw Carried out in extruder, during the melt blending mass ratio of the organic containing phosphorus-nitrogen of end sulfydryl-thioesters compound and PET section for 3~ 10:90~97, the temperature of the melt blending is 255~265 DEG C；

The technological parameter of the melt spinning is：

Extrusion temperature：280-290℃；

Chilling temperature：20-30℃；

Winding speed：2500-3500m/min；

Limited oxygen index >=38% of described fire-retardant polyester fibre POY, filament number be 0.3~1.0dtex, fracture strength >= 2.1cN/dtex, elongation at break is 110.0 ± 10.0%.